Use of dihydrobenzofuranones as perfuming ingredients

ABSTRACT

We describe the use of substituted (3H)-benzo b!furan-2-ones, namely with alkyl groups, for the preparation of perfuming compositions and perfumed articles, to which these compounds impart odor notes of the lactonic, coumarinic and fruity, or yet musky, type.

TECHNICAL FIELD

The present invention relates to the field of perfumery. It concerns, more particularly, the use, as a perfuming ingredient, of a compound of formula ##STR1## wherein a. symbols R¹ to R⁴ are identical or different and each represents a hydrogen atom, a saturated or unsaturated, linear or branched, alkyl radical having from 1 to 5 carbon atoms, a linear or branched alkoxy radical having from 1 to 4 carbon atoms, a cycloaliphatic radical having 5 or 6 carbon atoms, or an aromatic radical, which cyclic radical can possess one or several lower alkyl radicals as substituents;

or wherein

b. two adjacent symbols amongst the R¹ to R⁴ symbols are taken together to represent a saturated or unsaturated ring having 5 or 6 carbon atoms, which ring can possess one or several lower alkyl radicals as substituents, and the other two symbols represent hydrogen.

By a lower alkyl radical it is meant here a C₁ to C₄, linear or branched, alkyl radical and, more particularly, a methyl or ethyl radical.

PRIOR ART

The compounds of formula (I) are analogues of 3H-benzo b!furan-2-one, a compound of well-known structure. Furthermore, the structure of several compounds obeying formula (I) is also known from the prior art and several benzofuran-2(3H)-ones are known to possess therapeutical properties, namely as anti-inflamatory agents (see, for example, O. Piccolo et al., J. Chem. Res. 1985, 258). However, in spite of the interest that these compounds have aroused in the pharmaceutical field, we have been unable to find in the prior art any description, or even suggestion, related to the potential usefulness of such compounds in perfumery. Quite clearly, the odor properties of these compounds have gone totally unnoticed up until now.

DESCRIPTION OF THE INVENTION

Yet, we have now discovered that the compounds of formula (I) possess very useful odor properties and that, as a result, they can be used to prepare perfuming compositions and perfumed articles of varied nature.

The odor notes of compounds (I) do in fact cover a very wide spectrum of odoriferous nuances. Whereas certain compounds (I) develop a dominant note of the lactonic, coumarinic, hay type, reminiscent of the odor of flouve and the typical character of tonka beans, others develop notes which are rather lactonic and wherein the fruity, apricot-like character is dominant, or still other compounds develop a musky type odor, recalling the odor of the nitromusks (musk ketone, musk ambrette, etc), or a phenolic, crystalmoss type odor. In fact, certain compounds develop odors in which several of these characters are mixed.

It is therefore apparent that the use of compounds (I) in perfumery makes it possible to obtain a variety of perfuming effects and that these compounds can serve to impart or enhance the coumarinic, lactonic-fruity or even musky notes of the compositions into which they are incorporated.

The odor properties of these compounds are all the more surprising in that they are not represented in a similar way in other families of compounds whose structure is nevertheless very close to that of compounds (I). Thus, for example, we have observed that homologues of these compounds which do not possess a substituent in position 3 of the lactonic ring, or which have two substituents in the same position, turn out to be poor perfuming ingredients when compared to the corresponding compound (I), or are even totally devoid of an olfactive character. We have thus repeatedly observed that the presence of a single substituent in position 3 of the basic molecular skeleton, i.e. of the 3H-benzo b!furan-2-one type structure, appeared to be a required condition for these compounds to possess useful odor properties.

In this context, one can cite the case of 3,6-dimethyl-3H-benzo b!furan-2-one, the use of which in perfumery is preferred according to the invention. This lactone develops a very powerful coumarinic note, with a sweet, hay-like character reminiscent of the odor of flouve, as well as a vanilla and tonka type note. Yet, this combination of odor characters, and in particular the strength of the coumarinic-tonka character which renders this compound particularly precious for an alternative use to that of coumarine, is not represented in the weakly coumarinic and phenolic odor of 3,3,6-trimethyl-3H-benzo b!furan-2-one, and even less in that of 3-ethyl-3,6-dimethyl-3H-benzo b!furan-2-one, which possesses a disagreable odor typical of hydrocarbons. Moreover, it turned out that this hydrocarbon odor is also characteristic of the note of 3,6-dimethyl-3-propyl-3H-benzo b!furan-2-one, whereas 3-butyl-3,6-dimethyl-3H-benzo b!furan-2-one possesses a very weak odor with a vaguely lactonic character.

The same kind of behaviour was observed between 6-isopropyl-3-methyl-3H-benzo b!furan-2-one and its higher homologues doubly substituted in position 3. This novel lactone is thus a preferred compound of the invention, its odor being representative of the lactonic, fruity, apricot type dominant notes above-cited, accompanied in this case by a slightly phenolic undernote. It is in fact a very tenacious odor, recalling that of decalactone and Veloutone (2,2,5-trimethyl-5-pentyl-1-cyclopentanone; origin: Firmenich SA, Geneva, Switzerland). It was with surprise that the expert perfumers discovered that this olfactive richness had entirely disappeared in 6-isopropyl-3,3-dimethyl-3H-benzo b!furan-2-one, devoid of olfactive character, or yet in 3-ethyl-6-isopropyl-3-methyl-3H-benzo b!furan-2-one, 6-isopropyl-3-methyl-3-propyl-benzo b!furan-2-one and 3-butyl-6-isopropyl-3-methyl-3H-benzo b!furan-2-one, all of which possess very weak odors, with a vaguely musky or lactonic character.

The surprising olfactive superiority of compounds (I) with regard to their homologues was also very obvious in the case of 5,7-diisopropyl-3-methyl-3H-benzo b!furan-2-one and of 5,7-di-tert-butyl-3-methyl-3H-benzo b!furan-2-one. These two novel compounds, which are preferred objects of the invention, possess odors which are typical of the third olfactive family discovered amongst the compounds of the invention, i.e. the odors with a musky character. These odors are all the more unexpected in that they are of the nitromusk type, in spite of the absence of nitrogen-containing groups in the molecule. In particular, the above-mentioned di-tert-butylated lactone possesses a very powerful musky odor, reminiscent of that of the xylol and Baur musks. Another aspect of its musky note is also reminiscent of the odor of the musk ketone. This compound is in fact a choice perfuming ingredient and its olfactive value revealed itself as even richer upon its use in admixture with 3-methyl-cyclopentadec-5-en-1-one (see U.S. Pat. No. 5,354,735) or yet with other musky ingredients which do not possess the characteristic notes of the so-called "nitromusks", such as for example Tonalid® (7-acetyl-1,1,3,4,4,6-hexamethyltetraline; origin: PFW, Holland).

Again, in both cases, their lower homologues non-methylated in position 3, to wit 5,7-diisopropyl-3H-benzo b!furan-2-one and 5,7-di-tert-butyl-3H-benzo b!furan-2-one, as well as their di-methylated homologues, or 5,7-diisopropyl-3,3-dimethyl-3H-benzo b!furan-2-one and 5,7-di-tert-butyl-3,3-dimethyl-3H-benzo b!furan-2-one, have much too weak odors, devoid of a well-defined olfactive character.

Many other examples of the surprising olfactive behaviour of compounds (I) were observed. On the other hand, in addition to the remarkable range of odor nuances observed, certains types of lactones amongst the compounds (I) seemed to be the object of a particular preference from the perfumers.

In this context, there can be cited the compounds of formula ##STR2## wherein symbols R² and R³ are identical or different and represent each a hydrogen atom or a C₁ to C₄ linear or branched alkyl or alkoxy radical, a cycloaliphatic radical having 5 or 6 carbon atoms or an aromatic radical, wherein this cyclic radical can possess one or several lower alkyl radicals as substituents.

Examples of choice ingredients obeying formula (Ia) have already been cited, and others are indicated in Table I further on. As preferred ingredients, there will still be cited 3-methyl-6-phenyl-3H-benzo b!furan-2-one whose lactonic, fruity, apricot, slightly fatty odor, reminiscent of that of the δ-lactones, of γ-undecalactone and of Veloutone, and in particular its extraordinary tenacity, render it a particularly prized ingredient. The uncommon tenacity of the odor of this compound, the intensity of which remained unchanged on a smelling strip for more than a year, goes in fact far beyond that of any lactone known heretofore and renders this compound extremely advantageous for the typical applications of the cited known lactones.

Other useful examples amongst compounds (I), particularly preferred examples of which have already been cited, are the lactones of formula ##STR3## wherein R² and R⁴ are identical or different and represent each a linear or branched C₁ to C₄ alkyl or alkoxy radical, a cycloaliphatic radical having 5 or 6 carbon atoms or an aromatic radical, which cyclic radical can possess one or several lower alkyl radicals as substituents.

Finally, table I hereafter cites yet other preferred compounds and their olfactive characters.

                  TABLE I                                                          ______________________________________                                         No  Compound           Odor properties                                         ______________________________________                                         1   3-methyl-5-propyl-3H-benzo b!                                                                     lactonic, hay, flouve, bran                                 furan-2-one                                                                2   5-tert-butyl-3-methyl-3H-benzo b!                                                                 lactonic, powdery, woody,                                   furan-2-one        moss, particularly tenacious,                                                  reminiscent                                                                    of p-tert-butyl-cyclohexyl                                                     acetate                                                 3   3-methyl-5-(1-methylpropyl)-3H-                                                                   lactonic, fruity, peach and                                 benzo b!furan-one  raspberry, with a vanillic                                                     undernote, very powerful                                4   6-methoxy-3-methyl-3H-benzo b!                                                                    coumarinic, hay, flouve,                                    furan-2-one        powerful;                                                                      bottom note slightly phenolic                           5   3,6,7-trimethyl-3H-benzo b!furan-                                                                 coumarinic, lactonic,                                       2-one              slightly peach,                                                                slight phenolic nuance, with a                                                 powerful bottom note                                    6   3,5,6-trimethyl-3H-benzo b!furan-                                                                 coumarinic, lactonic, coconut                               2-one                                                                      7   3,4,6-trimethyl-3H-benzo b!furan-                                                                 coumarinic, reminiscent of the                              2-one              odor of bitter almonds, benzoic,                                               pleasant                                                8   3,5,6,7-tetrahydro-3-methyl-                                                                      lactonic, powerful, coconut,                                indeno 5,6-b!furan-2-one                                                                          flouve;                                                                        bottom note, coumarinic, tonka                          9   3-methyl-3H-benzo b!furan-one                                                                     tonka, coumarinic-dry,                                                         powerful                                                                       benzoic, sweet                                          10  6-ethyl-3-methyl-3H-benzo b!                                                                      lactonic, coumarinic, slightly                              furan-2-one        phenolic, crystalmoss,                                                         reminiscent                                                                    of the odor of lilac and                                                       Florex ®.sup.1)                                     ______________________________________                                          .sup.1) 9(10)ethylidene-3-oxatricylclo 6.2.1.0.sup.2,7 !undecan4-one;          origin: Firmenich SA, Geneva, Switzerland                                

As a result of their odor properties, compounds (I) are perfuming ingredients well adapted to both fine and technical perfumery applications. They are advantageous for the preparation of perfuming bases and compositions, perfumes and colognes, as well as for perfuming a variety of products such as soaps, bath or shower gels, shampoos and other hair-care products, body or air-deodorants and cosmetic preparations. One can also use them advantageously for perfuming detergents and fabric softeners, as well as household products.

In these applications, they can be used alone or, as is more current in the art, in admixture with other perfuming ingredients, solvents or adjuvants of current use in perfumery.

The concentrations in which they can be used depend on the nature of the desired fragrance effect, and on the nature of the coingredients with which they are admixed in the perfuming compositions and perfumed articles which contain them. Moreover, given the variety of odor nuances that can be found amongst compounds (I) and the spectrum of the corresponding odor intensities, it is clear that these concentrations will also depend on the nature of the compound (I) used. These concentrations can therefore vary in a very wide range of values, from which there can be cited, strictly by way of example, concentrations of the order of 1 to 10%, or even 20% or more by weight, relative to the weight of the composition into which they are incorporated, and this upon their use for preparing perfuming bases and compositions. Much lower concentration values will generally be used when these compounds serve to perfume the varied consumer products previously cited.

The perfuming compositions and perfumed articles containing compounds (I) and namely the preferred compounds already mentioned, are also the object of the invention.

In spite of the fact that several compounds obeying formula (I) are already known, frequently as a result of citations within the context of organic synthesis or relating to activities in the pharmacological field, there are many amongst these compounds which are novel chemical entities the useful odor properties of which could not have been anticipated from the prior art.

Another object of the invention is therefore a compound of formula ##STR4## such as defined in claim 1a., provided that the following combinations are excluded:

a. R¹ =R² =R³ =R⁴ =H;

b. R¹ =R² =R⁴ =H and R³ =methyl or methoxy or phenyl or 2-methylpropyl or cyclopentyl or cyclohexyl;

c. R¹ =R³ =R⁴ =H and R² =methyl or ethyl or phenyl;

d. R¹ =R⁴ =H, R² =CH₃ and R³ =cyclopentyl or cyclohexyl;

e. R¹ =R⁴ =H, R² =phenyl and R³ =methoxy; and

f. R¹ =R³ =methoxy, R² =CH₃ and R⁴ =H;

or such as defined in claim 1b., but excluding 1,5,8-trimethyl-1H-naphto 2,1-b!furan-2-one, 3-methyl-3H-naphto 2,3-b!furan-2-one and 1-methyl-1H-naphto 2,1-b!furan-2-one.

In addition, the invention relates in particular to the compounds selected from the group consisting of

a. 6-ethyl-3-methyl-3H-benzo b!furan-2-one;

b. 6-isopropyl-3-methyl-3H-benzo b!furan-2-one;

c. 3-methyl-5-propyl-3H-benzo b!furan-2-one;

d. 5-tert-butyl-3-methyl-3H-benzo b!furan-2-one;

e. 3-methyl-5-(1-methylpropyl)-3H-benzo b!furan-2-one;

f. 3,4,6-trimethyl-3H-benzo b!furan-2-one;

g. 3,5,6-trimethyl-3H-benzo b!furan-2-one;

h. 3,6,7-trimethyl-3H-benzo b!furan-2-one;

i. 3,5,6,7-tetrahydro-3-methyl-indeno 5,6-b!furan-2-one;

j. 5,7-diisopropyl-3-methyl-3H-benzo b!furan-2-one; and

k. 5,7-di-tert-butyl-3-methyl-3H-benzo b!furan-2-one.

The compounds of formula (I) can be prepared starting from phenolic derivatives which are either commercially available or which can be easily prepared from commercially available products. The starting phenolic derivatives can be converted in a manner analogous to the method described by O. Piccolo et al., cited ref., which is schematically represented as follows: ##STR5##

The formula (III) α-keto-ester wherein R=H, CH₃ is a commercial product.

Alternatively, and starting from the same phenolic derivatives of formula (II), compounds (I) can be prepared according to an original process which is also the object of the invention, characterized by the reaction of a phenolic derivative of formula ##STR6## wherein symbols R¹ to R⁴ are defined as in formula (I), with methylglyoxal, in the presence of an acidic catalyst and in an organic solvent susceptible of forming an azeotropic mixture with water.

The process of the invention is based on an original modification of the process described by R. W. Layer in J. Heterocycl. Chem. 12, 1067 (1975), represented in the following scheme: ##STR7##

We have established that, unlike the process of the invention, this known method did not enable the preparation, in an efficient manner, of the compounds having a lactonic ring substituted in position 3. One could then observe, in fact, the formation of a major amount of non-useful high molecular weight products.

Surprisingly, we discovered that when the reaction was carried out in an organic solvent capable of forming an azeotropic mixture with water, thus enabling elimination of the latter, the problem observed with the above-mentioned known process was solved.

As the acidic catalyst in the process according to the invention, there can be used an organic or a mineral acid of current use in this function, or yet an acidic resin. Preferably, sulfonic acids will be used, for example p-toluenesulfonic acid or sulfonic resins such asAmberlyst® (origin: Rohm & Haas Co.) or Dowex® (origin: Dow Chem. Co).

The organic solvents that can be used in this process belong to the hydrocarbons family, namely toluene, benzene, cyclohexane or yet xylene, or to that of the currently used chlorinated solvents. Very good yields were obtained with toluene, for example.

The reaction can be carried out at atmospheric pressure and at the solvent's reflux temperature, or under vacuum at a temperature adapted to the azeotropic distillation of water.

The phenolic derivatives of formula (II), as well as methylglyoxal, used as starting products, can be commercially obtained or easily prepared starting from commercial products, following conventional methods.

The invention will now be described in further detail by way of the following examples, wherein the temperatures are indicated in degrees centigrade and the abbreviations have the usual meaning in the art.

EMBODIMENTS OF THE INVENTION EXAMPLE 1

Preparation of compounds (I)

General method I (according to Circerio et al.)

The method described by O. Piccolo et al., cited ref., page 259 and by A. Citterio et al., Synthesis, 1984, page 763 was followed in an analogous manner, using the starting phenols indicated in the following table. The compounds were purified by means of the usual techniques, i.e. chromatography, distillation, etc. The homologues of compounds (I) non-methylated in position 3 are prepared in an analogous manner (see scheme I).

General method II (according to the invention)

A three-neck flask equipped with a Dean-Stark type water separator, a thermometer and an inlet funnel, is charged with 0.1 mole of phenol, 150 ml of toluene and 1.0 g of p-toluenesulfonic acid. The mixture is heated to reflux (110°) and 0.1 mole of methylglyoxal (40% aqueous solutions, Fluka) is slowly introduced (over 1h30) while maintaining reflux to eliminate the water. The mixture is heated to reflux for yet 1 h, then cooled to room temperature, the organic phase is washed with a saturated solution of NaHCO₃, then with water to neutrality, dried over Na₂ SO₄, concentrated and purified by column chromatography (SiO₂) and distillation or crystallization, depending on the case.

Of course, when methylglyoxal is replaced by glyoxal in this process, there are again obtained the corresponding lower homologues of the compounds of the invention, i.e. the lactones which are not substituted in position 3 of the lactonic ring.

On the other hand, the higher homologues of compounds (I) which are di-substituted in position 3 are prepared by alkylation, under known conditions, of the appropriate compounds of the invention.

Several of these homologue compounds, selected namely amongst those cited above, are also described hereinafter.

The following Table II cites the compounds prepared and their odor properties:

                  TABLE II                                                         ______________________________________                                                                         Odor properties                                No  Starting product                                                                             Final product of the final product                           ______________________________________                                         1   phenol        compound 9, Table I                                                                          see Table 1                                    2   4-methylphenol                                                                               3,5-dimethyl-3H-                                                                             strongly                                                         benzo b!furan-2-one                                                                          crystalmoss                                                                    phenolic, slightly                                                             coumarinic                                     3   3-methylphenol                                                                               3,6-dimethyl-3H-                                                                             see above                                                        benzo b!furan-2-one                                          4   2-methylphenol                                                                               3,7-dimethyl-3H-                                                                             dry, crystalmoss,                                                benzo b!furan-2-one                                                                          seaweed                                        5   3-ethylphenol compound 10, Table I                                                                         see Table I                                    6   4-ethylphenol 5-ethyl-3-methyl-3H-                                                                         crystalmoss,                                                     benzo b!furan-2-one                                                                          phenolic                                       7   4-propylphenol                                                                               compound 1, Table I                                                                          see Table I                                    8   3-isopropylphenol                                                                            6-isopropyl-3-methyl-                                                                        see above                                                        3H-benzo b!furan-2-                                                            one                                                          9   4-isopropylphenol                                                                            5-isopropyl-3-methyl-                                                                        phenolic, thyme                                                  3H-benzo b!furan-2-                                                                          leaves, lactonic                                                 one                                                          10  3-tert-butylphenol                                                                           6-tert-butyl-3-methyl                                                                        sweet, vanillic                                                  3-H-benzo b!furan-2-                                                           one                                                          11  4-tert-butylphenol                                                                           compound 2, Table I                                                                          see Table I                                    12  4-(1-methylpropyl)-                                                                          compound 3, Table I                                                                          see Table I                                        phenol                                                                     13  3-methoxyphenol                                                                              compound 4, Table I                                                                          see Table I                                    14  4-methoxyphenol                                                                              5-methoxy-3-methyl-                                                                          phenolic, weakly                                                 3H-benzo b!furan-2-                                                                          coumarinic, vanillic                                             one                                                          15  2,3-dimethylphenol                                                                           compound 5, Table I                                                                          see Table I                                    16  2,4-dimethylphenol                                                                           3,5,7-trimethyl-3H-                                                                          Florex ®,                                                    benzo b!furan-2-one                                                                          coumarinic                                                                     lactonic, flouve,                                                              rhubarb-metallic,                                                              fatty                                          17  3,4-dimethylphenol                                                                           compound 6, Table I                                                                          see Table I                                    18  3,5-dimethylphenol                                                                           compound 7, Table I                                                                          see Table I                                    19  2,4,5-trimethyl-                                                                             3,4,6,7-tetramethyl-                                                                         phenolic, waxy                                     phenol        3H-benzo b!furan-2-                                                            one                                                          20  3-phenylphenol                                                                               3-methyl-6-phenyl-                                                                           see above                                                        3H-benzo b!furan-2-                                                            one                                                          21  2-phenylphenol                                                                               3-methyl-7-phenyl-                                                                           phenolic,                                                        3H-benzo b!furan-2-                                                                          coumarinic                                                       one                                                          22  5,6,7,8-tetrahydro-1-                                                                        6,7,8,9-tetrahydro-3-                                                                        vaguely humus;                                     naphthalenol  methyl-3H-naphtho                                                                            bottom note                                                       1,2-b!furan-2-one                                                                           coumarinic, flouve,                                                            phenolic                                       23  5-indanol     compound 8, Table I                                                                          see Table 1                                    24  3,4,5,6-tetrahydro-                                                                          5,6,7,8-tetrahydro-                                                                          vaguely musky                                      3,3,4α,5β,6,6-hexa-                                                               3,5,5,6α7β,8,8-hepta-                                                             lactonic; bottom                                   methyl-1-naphtha-                                                                            methyl-3H-naphtho                                                                            note                                               lenol          2,3-b!furan-2-one                                                                           musky                                          25  2,4-di-tert-butyl                                                                            5,7-di-tert-butyl-3-                                                                         see above                                          phenyl        methyl-3H-                                                                     benzo b!furan-2-one                                          26  2,4-di-tert-butyl-3-                                                                         5,7-di-tert-butyl-3H                                                                         vaguely musky                                      phenol        benzo b!furan-2-one                                          27  5,7-di-tert-butyl-3-                                                                         5,7-di-tert-butyl-3,3-                                                                       weak, without                                      methyl-3H-    dimethyl-3H-  olfactive character                                benzo b!furan-2-one                                                                          benzo b!furan-2-one                                          28  2,4-diisoprophyl-                                                                            5,7-diisopropyl-3H-                                                                          without olfactive                                  phenol (see H.)                                                                              benzo b!furan-2-one                                                                          character                                          Jendralla et al.,                                                              Synthesis 1990, 827)                                                       29  2,4-diisopropyl-                                                                             5,7-diisopropyl-3-                                                                           see above                                          phenol        methyl-3H-                                                                     benzo b!furan-2-one                                          30  5,7-diisopropyl-3-                                                                           5,7-diisopropyl-3,3-                                                                         without olfactive                                  methyl-3H-    dimethyl-3H-  character                                          benzo b!furan-2-one                                                                          benzo b!furan-2-one                                          31  2-tert-butyl-4-ethyl-                                                                        7-tert-butyl-5-ethyl-3-                                                                      lactonic, coconut,                                 phenol        methyl-3H-    peach-slightly hay-                                              benzo b!furan-2-one                                                                          like                                           32  4-(1,1-       5-(1,1-       raspberry,                                         dimethylpropyl)-                                                                             dimethylpropyl)-3-                                                                           strawberry,                                        phenol        methyl-3H-    liqueur                                                          benzo b!furan-2-one                                          33  2-tert-butyl-phenol                                                                          7-tert-butyl-3-methyl-                                                                       green, pyrazines,                                                3H-benzo b!furan-2-                                                                          peas                                                             one                                                          34  3,6-dimethyl-3H-                                                                             3,3,6-trimethyl-3H-                                                                          see above                                          benzo b!furan-2-one                                                                          benzo b!furan-2-one                                          35  6-isopropyl-3-                                                                               6-isopropyl-3,3-                                                                             see above                                          methyl-3H-    dimethy-3H-                                                      benzo b!furan-2-one                                                                          benzo b!furan-2-one                                          36  6-isopropyl-3-                                                                               6-isopropyl-3-methyl-                                                                        see above                                          methyl-3H-    3-propyl-3H-                                                     benzo b!furan-2-one                                                                          benzo b!furan-2-one                                          ______________________________________                                    

The analytical characteristics of the compounds cited in this Table are described hereinafter following the same order:

    __________________________________________________________________________     Compound 1                                                                     Purity:       99.8%                                                            MS:           M.sup.+ 148(98); m/e: 133(2), 120(96), 103(4), 91                              (100), 77(10), 65(14), 51(15), 39(12)                            .sup.1 H-NMR (360 MHz, CDCl.sub.3):                                                          1.57(d: J=7, 3H), 3.72(q: J=7, 1H), 7.06-7.36                                  (m, 4H) δ ppm                                              .sup.13 C-NMR (90 MHz, CDCl.sub.3):                                                          1q: 15.9; 5d: 38.4, 110.7, 123.9, 124.2, 128.8; 3s:                            128.8, 153.5, 177.9 δ ppm                                  Compound 2                                                                     Purity        99.7%                                                            M.p.          37.5-39°                                                  MS:           M.sup.+ 162(72); m/e: 147(1), 134(100), 119(15), 105                           (14), 91(46), 77(14), 65(10), 51(12), 39(10)                     .sup.1 H-NMR (360 MHz, CDCl.sub.3):                                                          1.56(d: J=7, 3H), 2.35(s, 3H), 3.68(q: J=7, 1H),                               6.97 (d: J=7, 1H), 7.07(m, 2H) δ ppm                       .sup.13 C-NMR (90 MHz, CDCl.sub.3):                                                          2q: 15.9, 21.1; 4d: 38.5, 110.3, 124.4, 129.1; 4s:                             128.7, 133.8, 151.4, 178.3 δ ppm                           Compound 3                                                                     Purity        99.8%                                                            M.p.          41.5-43°                                                  MS:           M.sup.+ 162(82); m/e: 147(2), 134(100), 119(22), 105                           (16), 91(58), 77(14), 65(12), 51(12), 39(14)                     .sup.1 H-NMR (360 MHz, CDCl.sub.3):                                                          1.53(d: J=7, 3H), 2.37(s, 3H), 3.67(q: J=7, 1H),                               6.90(s, 1H), 6.95(d: J=7, 1H), 7.12(d: J=7, 1H) δ                        ppm                                                              .sup.13 C-NMR (90 MHz, CDCl.sub.3):                                                          2q: 16.0, 21.6; 4d: 38.2, 111.3, 123.5, 124.8; 4s:                             125.8, 139.2, 153.6, 178.3 δ ppm                           Compound 4                                                                     Purity        99.9%                                                            M.p.          33.5-35°                                                  MS:           M.sup.+ 162(70); m/e: 147(1), 134(100), 119(20), 105                           (15), 91(54), 77(14), 65(10), 51(12), 39(12)                     .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           1.56(d: J=7, 3H), 2.32(s, 3H), 3.72(q: J=7, 1H),                               7.01-7.12(m, 3H) δ ppm                                     .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           2q: 15.1, 15.9; 4d: 38.8, 121.1, 124.0, 130.2; 4s:                             121.0, 128.4, 152.0, 178.2 δ ppm                           Compound 5                                                                     Purity        98.7%                                                            MS:           M.sup.+ 176(45); m/e: 161(2), 148(66), 133(100), 115                           (8), 105(22), 91(17), 77(20), 65(12), 51(14), 39                               (20)                                                             .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           1.24(t: J=7, 3H), 1.55(d: J=7, 3H), 2.67(q: J=7,                               2H), 3.68(q: J=7, 1H), 6.95(s, 1H), 6.98(d: J=7,                               1H), 7.15(d: J=7, 1H) δ ppm                                .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           2q: 15.6, 16.0; 1t: 29.1; 4d: 38.3, 110.1, 2×123.6;                      4s:                                                                            126.0, 145.7, 153.7, 178.4 δ ppm                           Compound 6                                                                     Purity        99.1%                                                            MS:           M.sup.+ 176(31); m/e: 161(2), 148(30), 133(100), 115                           (4), 105(8), 91(11), 77(16), 65(8), 51(12), 39(12)               .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           1.23(t: J=7, 3H), 1.57(d: J=7, 3H), 2.64(q: J=7,                               2H), 3.70(q: J=7, 1H), 6.99(d: J=7, 1H), 7.10(m,                               2H) δ ppm                                                  .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           2q: 15.9, 16.0; 1t: 28.6; 4d: 38.5, 110.3, 123.3, 128.0;                       4s: 128.8, 140.4, 151.5, 178.3 δ ppm                       Compound 7                                                                     Purity        99.2%                                                            MS:           M.sup.+ 190(17); m/e: 161(14), 146(1), 133(100), 115                           (4), 103(5), 91(5), 77(7), 65(2), 51(2), 39(1)                   .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           0.94(t: J=7, 3H), 1.57(d: J=7, 3H), 1.63(m, 2H),                               2.58(t: J=7, 2H), 3.70(q: J=7, 1H), 6.99(d: J=7,                               1H), 7.07(m, 2H) δ ppm                                     .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           2q: 13.7, 15.9; 2t: 24.9, 37.7; 4d: 38.5, 110.2, 123.8,                        128.7; 4s: 128.6, 138.8, 151.6, 178.3 δ ppm                Compound 8                                                                     Purity        99.4%                                                            MS:           M.sup.+ 190(44); m/e: 175(12), 162(33), 147(100), 128                          (6), 119(14), 103(8), 91(32), 77(14), 65(10),                                  51(6), 39(8)                                                     .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           1.25(d: J=7, 6H), 1.55(d: J=7, 3H), 2.93(sept.:                                J=7, 1H), 3.69(q: J=7, 1H), 6.97(s, 1H), 7.01(d:                               J=7, 1H), 7.17(d: J=7, 1H) δ ppm                           .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           3q: 15.9; 2×24.0; 5d: 34.4, 38.3, 128.6, 122.3,                          123.6;                                                                         4s: 126.1, 150.5, 153.7, 178.3 δ ppm                       Compound 9                                                                     Purity        99.4%                                                            MS:           M.sup.+ 190(20); m/e: 175(24), 162(8), 147(100), 128                           (4), 115(6), 103(4), 91(16), 77(8), 65(4), 51(3), 39                           (2)                                                              .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           1.25(d: J=7, 6H), 1.57(d: J=7, 3H), 2.91(sept.:                                J=7, 1H), 3.70(q: J=7, 1H), 7.01(d: J=7, 1H),                                  7.13(m, 2H) δ ppm                                          .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           3q: 15.9; 2×24.3; 5d: 34.0, 38.6, 110.3, 121.8,                          126.6;                                                                         4s: 128.7, 145.1, 151.6, 178.3 δ ppm                       Compound 10                                                                    Purity        99.3%                                                            M.p.          73-75°                                                    MS:           M.sup.+ 204(30); m/e: 189(84), 176(6), 161(100), 146                           (5), 133(29), 115(18), 105(12), 91(21), 77(10), 65                             (6), 51(4), 41(4)                                                .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           1.32(s, 9H), 1.54(d: J=7, 3H), 3.67(q: J=7, 1H),                               7.11-7.20(m, 3H) δ ppm                                     .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           4q: 15.9, 3×31.3; 4d: 38.2, 107.9, 121.0, 123.3; 5s:                     35.1, 125.7, 152.9, 153.6, 178.3 δ ppm                     Compound 11                                                                    Purity        100%                                                             M.p.          71-72°                                                    MS:           M.sup.+ 204(28); m/e: 189(88), 161(100), 146(3), 133                           (14), 115(8), 105(5), 91(10), 77(6), 65(4), 51(4),                             41(5)                                                            .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           1.33(s, 9H), 1.58(d: J=7, 3H), 3.70(q: J=7, 1H),                               7.01(d: J=7, 1H), 7.27(s, 1H), 7.31(d: J=7, 1H)                                δ ppm                                                      .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           4q: 15.9, 3×31.6; 4d: 38.7, 110.0, 120.8, 125.6; 5s:                     34.7, 128.3, 147.4, 151.3, 178.4 δ ppm                     Compound 12   (1:1 mixture of two diastereoisomers)                            Purity        98.1%                                                            MS:           M.sup.+ 204(18); m/e: 189(2), 175(79), 161(5), 147                             (100), 133(8), 115(8), 103(4), 91(14), 77(6), 65                               (3), 51(2), 39(2)                                                .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           0.83(t: J=7, 3H), 2.23(d: J=7, 3H), 1.57(d: J=7,                               3H), 1.60(m, 2H), 2.49(hex.: J =7, 1H), 3.70(q:                                J=7, 1H), 6.96-7.13(m, 3H) δ ppm                           .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           3q: 12.2, 15.9, 22.0/22.1; 1t: 31.3/31.4; 5d: 38.6,                            41.5, 110.3, 122.3/122.4, 127.2/127.3; 4s: 128.7,                              143.9, 151.6, 178.3 δ ppm                                  Compound 13                                                                    Purity        96.5%                                                            M.p.          33-35°                                                    MS:           M.sup.+ 178(64); m/e: 163(12), 150(100), 135(20), 121                          (17), 107(22), 91(22), 77(26), 65(12), 51(10), 39                              (8)                                                              .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           1.53(d: J=7, 3H), 3.67(q: J=7, 1H), 3.80(s, 3H),                               6.65(s, 1H), 6.67(d: J=7, 1H), 7.13(d: J=7, 1H)                                δ ppm                                                      .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           2q: 16.2, 55.6; 4d: 38.0, 97.5, 109.7, 124.3; 4s: 120.5,                       154.4, 160.4, 178.4 δ ppm                                  Compound 14                                                                    Purity        99.5%                                                            M.p.          63-65°                                                    MS:           M.sup.+ 178(48); m/e: 163(1), 150(92), 135(100), 121                           (3), 107(20), 91(10), 77(30), 63(11), 53(20), 39                               (14)                                                             .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           1.57(d: J=7, 3H), 3.71(q: J=7, 1H), 3.80(s, 3H),                               6.81(m, 2H), 7.01(d: J=7, 1H) δ ppm                        .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           2q: 15.9, 55.9; 4d: 39.0, 110.2, 111.1, 113.5; 4s:                             129.8, 147.3, 156.7, 178.3 δ ppm                           Compound 15                                                                    Purity        99.8%                                                            MS:           M.sup.+ 176(47); m/e: 161(2), 148(100), 133(53), 115                           (16), 105(62), 91(26), 77(22), 65(10), 51(10), 39(8)             .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           1.54(d: J=7, 3H), 2.22(s, 3H), 2.29(s, 3H), 3.71                               (q: J=7, 1H), 6.93(d: J=7, 1H), 6.97(d: 7, 1H)                                 δ ppm                                                      .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           3q: 11.8, 16.1, 19.6; 3d: 39.0, 120.5, 125.1; 5s: 119.7,                       125.8, 137.9, 152.2, 178.5 δ ppm                           Compound 16                                                                    Purity        99.3%                                                            M.p.          30-32°                                                    MS:           M.sup.+ 176(46); m/e: 161(1), 148(100), 133(58), 115                           (12), 105(54), 91(24), 77(24), 65(10), 51(10), 39                              (10)                                                             .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           1.53(d: J=7, 3H), 2.27(s, 3H), 2.31(s, 3H), 3.67                               (q: J=7, 1H), 6.87(s, 1H), 6.90(s, 1H) δ ppm               .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           3q: 14.9, 16.0, 21.0; 3d: 38.9, 121.6, 130.7; 5s: 120.5,                       128.3, 133.5, 149.9, 178.5 δ ppm                           Compound 17                                                                    Purity        100%                                                             M.p.          74-75°                                                    MS:           M.sup.+ 176(60); m/e: 161(2), 148(100), 133(66), 115                           (10), 105(40), 91(17), 77(16), 65(5), 51(4), 39(4)               .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           1.51(d: J=7, 3H), 2.23(s, 3H), 2.25(s, 3H), 3.62                               (q: J=7, 1H), 6.84(s, 1H), 7.00(s, 1H) δ ppm               .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           3q: 16.0, 19.4, 20.1; 3d: 38.3, 111.6, 124.8; 5s: 126.0,                       132.2, 137.3, 151.8, 178.5 δ ppm                           Compound 18                                                                    Purity        99.8%                                                            M.p.          66-68°                                                    MS:           M.sup.+ 176(69); m/e: 161(8), 148(100), 133(70), 115                           (18), 105(80), 91(26), 77(29), 65(11), 51(12), 39                              (13)                                                             .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           1.56(d: J=7, 3H), 2.29(s, 3H), 2.32(s, 3H), 3.64                               (q: J=7, 1H), 6.73(s, 1H), 6.75(s, 1H) δ ppm               .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           3q: 15.6, 18.2, 21.5; 3d: 38.0, 108.8, 126.3; 5s: 124.0,                       134.5, 138.9, 153.6, 178.5 δ ppm                           Compound 19                                                                    Purity        100%                                                             M.p.          49-51°                                                    MS:           M.sup.+ 190(54); m/e: 175(5), 162(100), 147(78), 129                           (9), 119(56), 105(10), 91(32), 77(17), 65(10), 51                              (7), 39(8)                                                       .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           1.57(d: J=7, 3H), 2.17(s, 3H), 2.24(s, 3H), 2.26(s,                            3H), 3.67(q: J=7, 1H), 6.73(s, 1H) δ ppm                   .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           4q: 11.6, 15.7, 17.9, 19.4; 2d: 38.8, 126.6; 6s: 116.8,                        123.9, 131.2, 137.6, 152.0, 178.7 δ ppm                    Compound 20                                                                    Purity        99.6%                                                            M.p.          102-104°                                                  MS:           M.sup.+ 224(62); m/e: 209(2), 196(100), 181(10), 167                           (44), 152(36), 139(8), 128(6), 115(12), 102(6), 89                             (9), 76(8), 63(5), 51(4), 39(2)                                  .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           1.58(d: J=7, 3H), 3.73(q: J=7, 1H), 7.23-7.58                                  (m, 8H) δ ppm                                              .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           1q: 15.9; 9d: 38.3, 109.4, 123.0, 124.1, 2×127.1,                        127.8, 2×128.9; 5s: 127.6, 140.2, 142.5, 154.0,                          177.9                                                                          δ ppm                                                      Compound 21                                                                    Purity        99.3%                                                            M.p.          99-102°                                                   MS:           M.sup.+ 224(62); m/e: 196(52), 181(100), 165(22), 152                          (30), 139(6), 128(4), 115(12), 98(6), 89(4), 76(6),                            63(6), 51(4), 39(4)                                              .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           1.63(d: J=7, 3H), 3.79(q: J=7, 1H), 7.23(m, 2H),                               7.37(m, 1H), 7.46(m, 3H), 7.67(m, 2H) δ ppm                .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           1q: 16.0; 9d: 38.4, 122.7, 124.6, 127.9., 3×128.6,                       2×                                                                       128.9; 5s: 125.0, 129.5, 135.4, 150.5, 177.9 δ ppm         Compound 22                                                                    Purity        98.5%                                                            M.p.          63-65°                                                    MS:           M.sup.+ 202(60); m/e: 187(1), 174(100), 159(66), 145                           (28), 131(33), 115(33), 103(10), 91(22), 77(16), 65                            (8), 51(8), 39(6)                                                .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           1.52(d: J=7, 3H), 1.78(m, 4H), 2.72(m, 4H), 3.64                               (q: J=7, 1H), 6.85(d: J=7, 1H), 6.96(d: J=7, 1H)                               δ ppm                                                      .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           1q: 16.0; 4t: 22.2, 2×22.8, 29.4; 3d: 38.7, 120.3,                       124.5; 5s: 120.8, 125.1, 138.5, 151.5, 178.6 δ ppm         Compound 23                                                                    Purity        97.6%                                                            M.p.          79-81°                                                    MS:           M.sup.+ 188(52); m/e: 173(2), 160(100), 145(18), 133                           (14), 115(22), 103(4), 91(12), 77(8), 163(4), 51(4),                           39(2)                                                            .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           1.53(d: J=7, 3H), 2.10(m, 2H), 2.89(m, 4H), 3.67                               (q: J=7, 1H), 6.95(s, 1H), 7.09(s, 1H) δ ppm               .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           1q: 16.2; 3t: 25.8, 32.4, 33.2; 3d: 38.6, 107.0, 119.6;                        5s: 126.6, 139.7, 144.9, 152.1, 178.7 δ ppm                Compound 24   (1:1 mixture of two diastereoisomers)                            Purity        98%                                                              M.p.          127-130°                                                  MS:           M.sup.+ 286(29); m/e: 271(91), 243(4), 229(48), 215                            (100), 201(30), 187(12), 171(6), 157(5), 141(8),                               128(10), 115(8), 91(7), 77(6), 57(23), 43(12)                    .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           0.98(d: J=6, 6H), 1.10(s, 6H), 1.30(s, 6H), 1.57                               (m, 5H), 3.68(m, 1H), 7.07(s, 1H), 7.23(s, 1H)                                 δ ppm                                                      .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           7q: 13.9, 14.0, 15.9/16.0, 25.6/25.7, 25.8, 29.6/29.8,                         29.8/29.9; 5d: 38.4/38.5, 39.1, 39.2, 108.4,                                   122.4/122.5; 7s: 2×38.0, 126.2, 141.7, 146.9, 151.6,                     178.6 δ ppm                                                Compound 25                                                                    Purity        99.6%                                                            M.p.          62-64°                                                    MS:           M.sup.+ 260(26); m/e: 245(100), 232(2), 217(70), 201                           (2), 189(2), 175(2), 159(2), 145(2), 128(4), 115                               (6), 105(4), 91(6), 77(4), 57(9), 41(5)                          .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           1.33(s, 9H), 1.40(s, 9H), 1.57(d: 7, 3H), 3.67                                 (q: J=7, 1H), 7.11(s, 1H), 7.27(s, 1H) δ ppm               .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           7q: 15.9, 3×29.6, 3×31.6; 3d: 38.2, 118.2,                         122.8; 7s:                                                                     34.4, 34.8, 128.6, 133.3, 147.0, 149.2, 178.6 δ ppm        Compound 26                                                                    Purity        99.6%                                                            M.p.          89-92°                                                    MS:           M.sup.+ 246(22); m/e: 231(100), 217(1), 203(52), 188                           (2), 175(3), 161(6), 145(7), 128(6), 115(10), 105                              (8), 91(12), 80(9), 65(4), 57(6), 41(8)                          .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           1.32(s, 9H), 1.40(s, 9H), 3.68(s, 2H), 7.15(s, 1H),                            7.26(s, 1H) δ ppm                                          .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           6q: 3×29.6, 3×31.6; 1t: 32.9; 2d: 119.1, 122.7;                    7s:                                                                            34.3, 34.7, 123.0, 133.3, 146.8, 150.5, 174.5 δ ppm        Compound 27                                                                    Purity        99.3%                                                            M.p.          114-115°                                                  MS:           M.sup.+ 274(26); m/e: 259(90), 231(100), 215(4), 201                           (2), 189(2), 173(2), 159(2), 141(4), 128(6), 115                               (7), 108(7), 94(9), 80(10), 65(4), 57(18), 41(14)                .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           1.33(s, 9H), 1.40(s, 9H), 1.49(s, 6H), 7.05(split s,                           1H), 7.26(split s, 1H) δ ppm                               .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           8q: 2×25.5, 3×29.7, 3×31.7, 2d: 116.9,                       122.6; 8s:                                                                     34.4, 34.9, 42.5, 133.3, 133.5, 147.1, 147.9, 181.6                            δ ppm                                                      Compound 28                                                                    Purity:       99.5%                                                            M.p.          29-31°                                                    MS:           M.sup.+ 218(41); m/e: 203(100), 190(4), 175(89), 159                           (3), 147(27), 131(6), 119(14), 105(13), 91(19), 77                             (13), 65(7), 51(6), 41(10)                                       .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           1.23(d: J=7, 6H), 1.28(d: J=7, 6H), 2.88(sept.:                                J=7, 1H), 3.15(sept.: J=7, 1H), 3.69(s, 2H), 6.98                              (s, 1H) δ ppm                                              .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           4q: 2×22.4, 2×24.3; 1t: 33.4; 4d: 28.8, 34.1,                      119.6,                                                                         124.4; 5s: 122.7, 131.4, 145.1, 150.4, 174.8 δ ppm         Compound 29                                                                    Purity        99.5%                                                            MS:           M.sup.+ 232(27); m/e: 217(32), 204(16), 189(100), 175                          (3), 161(13), 147(6), 128(8), 115(10), 105(5), 91                              (13), 77(8), 65(4), 53(4), 41(9)                                 .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           1.24(d: J=7, 6H), 1.29(split d: J=7, 6H), 1.57(d:                              J=7, 3H), 2.49(sept.: J=7, 1H), 3.15(sept.: J=7,                               1H), 3.69(q: J=7, 1H), 6.93(s, 1H), 7.01(s, 1H)                                δ ppm                                                      .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           5q: 15.91 22.3, 22.5, 24.3, 24.4; 5d: 28.8, 34.1, 38.8,                        118.8, 124.3; 5s: 128.4, 131.3, 145.1, 149.1, 178.7                            δ ppm                                                      Compound 30                                                                    Purity        99.3%                                                            M.p.          34-37°                                                    MS:           M.sup.+ 246(29); m/e: 231(21), 218(24), 203(100), 187                          (2), 175(8), 161(3), 147(3), 128(7), 115(8), 105                               (5), 91(8), 80(6), 65(4), 53(3), 41(9)                           .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           1.25(d: J=7, 6H), 1.29(d: J=7, 6H), 1.49(s, 6H),                               2.90(sept.: J=7, 1H), 3.17(sept.: J=7, 1H), 6.88                               (split s, 1H), 7.00(split s, 1H) δ ppm                     .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           6q: 2×22.5, 2×24.3, 2×25.5; 4d: 28.7,                        34.2, 117.7,                                                                   124.0; 6s: 43.2, 131.4, 133.3, 145.2, 147.8, 181.7                             δ ppm                                                      Compound 31                                                                    Purity:       99.8%                                                            M.p.          57-58°                                                    MS:           M.sup.+ 232(24); m/e: 217(30), 204(6), 189(100), 175                           (10), 161(16), 141(4), 128(8), 115(8), 105(5), 91                              (10), 77(6), 65(4), 53(2), 41(4)                                 .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           1.23(t: J=7, 3H), 1.39(s, 9H), 1.56(d: J=7, 3H),                               2.63(q: J=7, 2H), 3.65(q: J=7, 1H), 6.93(s, 1H),                               7.05(s, 1H) δ ppm                                          .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           5q: 15.9, 16.0, 3×29.6; 1t: 28.8; 3d: 38.0, 120.6,                       125.4; 6s: 34.2, 129.2, 133.8, 140.0, 149.4, 178.5                             δ ppm                                                      Compound 32                                                                    Purity        96.8%                                                            M.p.          30-32°                                                    MS:           M.sup.+ 218(10); m/e: 203(4), 189(100), 175(4), 161                            (88), 145(4), 133(20), 115(10), 105(6), 91(12), 77                             (6), 65(3), 55(2), 41(3)                                         .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           0.69(t: J=7, 3H), 1.28(s, 6H), 1.59(d: J=7, 3H),                               1.63(q: J=7, 2H), 3.71(q: J=7, 1H), 7.01(d: J=7,                               1H), 7.20(s, 1H), 7.25(d: J=7, 1H) δ ppm                   .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           3q: 9.1, 16.0, 28.7; 1t: 37.0; 4d: 38.7, 109.9, 121.4,                         126.3; 5s: 37.9, 128.3, 145.8, 151.3, 178.4 δ ppm          Compound 33                                                                    Purity:       98.3%                                                            MS:           M.sup.+ 204(21); m/e: 189(34), 176(1), 161(100), 147                           (4), 133(26), 115(10), 105(6), 91(10), 77(6), 65                               (3), 51(2), 39(2)                                                .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           1.40(s, 9H), 1.57(d: J=7, 3H), 3.69(q: J=7, 1H),                               7.07-7.27(m, 3H) δ ppm                                     .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           4q: 15.9, 3×29.6; 4d: 37.9, 121.4, 124.0, 125.9; 5s:                     34.2, 129.2, 134.4, 151.4, 178.1 δ ppm                     Compound 34                                                                    Purity        99.9%                                                            MS:           M.sup.+ 176(60); m/e: 161(14), 148(100), 133(69), 115                          (15), 105(58), 91(16), 77(24), 63(10), 51(14), 39                              (18)                                                             .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           1.47(s, 6H), 2.37(s, 3H), 6.93(s, 1H), 6.96(d: J=7,                            1H), 7.09(d: J=7, 1H) δ ppm                                .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           3q: 21.6, 2×25.3; 3d: 111.4, 122.4, 124.9; 5s: 42.8,                     130.7, 138.9, 152.3, 181.2 δ ppm                           Compound 35                                                                    Purity        99.9%                                                            M.p.          77-78°                                                    MS:           M.sup.+ 204(39); m/e: 189(16), 176(64), 161(100), 145                          (4), 133(15), 115(13), 105(9), 91(16), 77(12), 65                              (8), 51(8), 41(14)                                               .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           1.26(d: J=7, 6H), 1.48(s, 6H), 2.93(sept.: J=7,                                1H), 6.99(s, 1H), 7.02(d: J=7, 1H), 7.12(d: J=7,                               1H) δ ppm                                                  .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           4q: 2×24.0, 2×25.3; 4d: 34.4, 108.8,                               2×122.4; 5s:                                                             42.9, 130.9, 150.2, 152.4, 181.4 δ ppm                     Compound 36                                                                    Purity        99.9%                                                            MS:           M.sup.+ 232(30); m/e: 217(3), 204(5), 189(100), 175                            (14), 161(36), 147(26), 133(10), 115(13), 105(9),                              91(16), 77(8), 65(5), 51(4), 41(14)                              .sup.1 H-NMR(360 MHz, CDCl.sub.3):                                                           0.83(t: J=7, 3H), 0.93-1.22(m, 2H), 1.27(d: J=7,                               6H), 1.47(s, 3H), 1.75(m, 1H), 1.90(m, 1H), 2.93                               (sept.: J=7, 1H), 6.97(split s, 1H), 7.01(split d,                             7, 1H), 7.08(d: J=7, 1H) δ ppm                             .sup.13 C-NMR(90 MHz, CDCl.sub.3):                                                           4q: 14.0, 2×24.0, 24.4; 2t: 18.1, 41.4; 4d: 34.3,                        108.6,                                                                         122.3, 122.7; 5s: 47.4, 129.4, 150.1, 152.9, 181.0                             δ ppm                                                      __________________________________________________________________________

EXAMPLE 2

Preparation of a perfuming composition

A base perfuming composition intended for a perfume of the masculine, oriental type, was prepared by admixing the following ingredients:

    ______________________________________                                         Ingredients           Parts by weight                                          ______________________________________                                         Linalyly acetate      210                                                      10%* Ambrox ® DL.sup.1)                                                                          350                                                      Dist. methyl anthranilate                                                                            25                                                       10%* 4(4-Hydroxyphenyl)-2-butanone                                                                   15                                                       Synth. bergamot oil   135                                                      10%* Ceylan cinnamon oil                                                                             70                                                       10%* Eugenol          40                                                       Lemon essential oil   110                                                      Heliotropine ord.     120                                                      Hydroxycitronellal    35                                                       10%* Purif. indol     15                                                       Polywood ®.sup.2) 190                                                      Dihydromyrcenol.sup.3)                                                                               180                                                      Linalol               50                                                       Lyral ®.sup.4)    400                                                      Synth. mandarin oil   30                                                       Iralia ®.sup.5)   90                                                       Methylnaphthylketone cryst.                                                                          20                                                       Methyl jasmonate      300                                                      Patchouli essential oil                                                                              120                                                      Sandalore ®.sup.6)                                                                               50                                                       Tonalid ®.sup.7)  500                                                      Exaltolide ®.sup.8)                                                                              200                                                      Vanilline             95                                                       Vertofix coeur.sup.9) 250                                                      TOTAL                 3600                                                     ______________________________________                                          *in dipropyleneglycol (DIPG)                                                   .sup.1) tetramethylperhydronaphthofuran, origin: Firmenich SA, Geneva,         Switzerland                                                                    .sup.2) perhydro5,5,8a-trimethyl-2-naphthyl acetate; origin: Firmenich SA      Geneva, Switzerland                                                            .sup.3) origin: International Flavors and Fragrances Inc., U.S.A.              .sup.4) 4(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde;            origin: International Flavors and Fragrances Inc., U.S.A.                      .sup.5) methylionone; origin: Firmenich SA, Geneva, Switzerland                .sup.6) 5(2,2,3-trimethylcyclopent-3-enyl)-3-methylpentan-2-ol; origin:        GivaudanRoure, Vernier, Switzerland                                            .sup.7) 7acetyl-1,1,3,4,4,6-hexamethyltetraline; origin: PFW, Holland          .sup.8) pentadecanolide; origin: Firmenich SA, Geneva, Switzerland             .sup.9) origin: International Flavors and Fragrances Inc., U.S.A.        

When there were added to this base composition of the balsamic, floral, woody, musky type, 400 parts by weight of 3,6-dimethyl-3H-benzo b!furan-2-one, there was obtained a novel composition with a distinctly enhanced oriental, coumarinic-vanilla note, with a well-defined tonka character and a clearly enhanced strength. This coumarinic olfactive effect, which was also observed at lower concentrations of the compound of the invention, of the order of a half or even a quarter of the cited amount, ressembles the effect that could have been obtained with coumarine, although the tonka beans type of note was more marked.

Similar effects, albeit with varied nuances, were obtained when the same amount of other compounds according to the invention, having a coumarinic odor, was added. For example, 3-methyl-3H-benzo b!furan-2-one imparted an odor of the same type, but drier and sweeter, whereas 6-methoxy-3-methyl-3H-benzo b!furan-2-one imparted to the composition a coumarinic odor with an enhanced phenolic character. The addition of 3,5,6,7-tetrahydro-3-methyl-indeno 5,6-b!furan-2-one also emphasized the coumarinic-tonka note in the odor of the new composition, with a coconut type top character, which could also be found when there was added 3,5,6-trimethyl-3H-benzo b!furan-2-one to the base composition, whereas 3,4,6-trimethyl-3H-benzo b!furan-2-one imparted a coumarinic-bitter almond note instead to this composition.

EXAMPLE 3

Perfuming of textiles

There were prepared samples of a perfumed softener base by adding to distinct samples of an unperfumed standard fabric softener the compounds according to the invention cited in the following Table, in the amounts indicated:

    __________________________________________________________________________                       Sample                                                       Ingredients       1  2  3  4  5  6  7                                          __________________________________________________________________________     unperfumed softener                                                                              99.9                                                                              99.9                                                                              99.9                                                                              99.9                                                                              99.9                                                                              99.9                                                                              99.9                                       3,6-dimethyl-3H-benzo b!furan-2-one                                                              0.1                                                                               -- -- -- -- -- --                                         6-isopropyl-3-methyl-3H-benzo b!                                                                 -- 0.1                                                                               -- -- -- -- --                                         furan-2-one                                                                    3-methyl-6-phenyl-3H-benzo b!                                                                    -- -- 0.1                                                                               -- -- -- --                                         furan-2-one                                                                    6-ethyl-3-methyl-3H-benzo b!furan-                                                               -- -- -- 0.1                                                                               -- -- --                                         2-one                                                                          6-methoxy-3-methyl-3H-benzo                                                                      -- -- -- -- 0.1                                                                               -- --                                          b!furan-2-one                                                                 5,7-diisopropyl-3-methyl-3H-benzo                                                                -- -- -- -- -- 0.1                                                                               --                                          b!furan-2-one                                                                 5,7-di-tert-butyl-3-methyl-3H-benzo                                                              -- -- -- -- -- -- 0.1                                         b!furan-2-one                                                                 __________________________________________________________________________

Seven batches of standard textiles, containing cotton, acrylic and nylon fabrics, were separately treated in seven fabric washing machines with respectively samples 1 to 7 prepared above. The seven textile batches thus treated were then evaluated on a blind test by a panel of expert perfumers, both wet and after drying.

According to the perfumers, three distinct fragrance effects could be observed. Thus, the textiles treated with samples 1, 4 and 5 developed an odor having a dominant coumarinic character, very powerful in the case of the batch treated with sample 1, with a distinctly marked hay, flouve and tonka character, whereas the batch treated with sample 4 developed an odor wherein the lactonic, crystalmoss character was more pronounced and which was also more phenolic.

As for the textiles treated with samples 2 and 3, their odor no longer had a dominant coumarinic character, but rather lactonic and fruity, very pleasant, recalling the fragrance developed by Veloutone (origin: Firmenich SA, Geneva, Switzerland) and the decalactones, and whose fruity note was similar to the odor of apricot. Furthermore, the textiles treated with sample 3 turned out to have a particularly tenacious odor, which stayed on the linen for a long time.

On the other hand, the batches treated with samples 6 and 7 were judged to be entirely different from the others, their odor being strongly musky and not at all coumarinic nor lactonic-fruity, with a much appreciated nitromusk type character.

This effect was all the more powerful in the textiles perfumed by means of sample 7, and this both when just out of the machine and 24 h later. The perfumers judged that these variations in the observed odor effects were totally surprising when they found out the nature of the perfuming ingredients used and the similarity of their structures.

EXAMPLE 4

Perfuming composition

A base perfuming composition intended for a powder detergent was prepared by admixing the following ingredients:

    ______________________________________                                         Ingredients               Parts by weight                                      ______________________________________                                         Benzyl acetate            50                                                   Linalyl acetate           20                                                   Phenylethyl acetate       40                                                   Verdyl acetate            100                                                  10%* Undecylenic aldehyde 70                                                   Hexylcinnamic aldehyde    80                                                   10%* Methyl benzoate      50                                                   Eugenol                   25                                                   Helional                  50                                                   10%* 4,4a,5,9b-Tetrahydro-indeno 1,2-d!-1,3-dioxine                                                      50                                                   Iralia ®.sup.1)       60                                                   Iso E Super.sup.2)        40                                                   Lilial ®.sup.3)       400                                                  Linalol                   100                                                  10%* Methylacetophenone   20                                                   10%* Methyl-p-cresol      10                                                   10%* Rose oxide           5                                                    10%* Phenylethyl methyl ether                                                                            10                                                   Phenethylol               210                                                  p-tert-Butyl-cyclohexanone acetate                                                                       170                                                  Benzyl salicylate         30                                                   Tonalid ®.sup.4)      160                                                  TOTAL                     1750                                                 ______________________________________                                          *in dipropyleneglycol (DIPG)                                                   .sup.1) methylionone; origin: Firmenich SA, Geneva, Switzerland                .sup.2) 2acetyl-1,2,3,4,6,7,8-octahydro-2,3,8,8-tetramethyl-naphthalene;       origin: IFF, USA                                                               .sup.3) 2methyl-3-(4-tert-butyl-1-phenyl)-propanal; origin: GivaudanRoure      Vernier, Switzerland                                                           .sup.4) 7acetyl-1,1,3,4,4,6-hexamethyltetraline; origin: PFW, Holland    

250 Parts by weight of 5,7-di-tert-butyl-3-methyl-3H-benzo b!furan-2-one were added to this base composition. A novel composition was thus obtained, the musky, earthy, aromatic note of which, imparted by Tonalid®, was distinctly enhanced relative to that of the base composition, its odor having become musky-animal and clearly evoking the typical fragrance effect that could have been obtained by adding Musk Xylol to the base composition.

On the other hand, when the base composition contained, instead of Tonalid®, 60 parts by weight of 3-methyl-cyclopentadec-5-en-l-one (see U.S. Pat. No. 5,354,735), thus having already a musky, nitromusk and powdery character, the addition of 350 parts by weight of the above-mentioned compound of the invention made it possible to obtain a novel composition wherein the above-mentioned olfactive effect was even more obvious, the odor of the composition being even more reminiscent of the fragrance that can be obtained with such known compounds as Musk Xylol, Musk Baur or yet Musk ketone.

Furthermore, when 250 parts by weight of 5,7-diisopropyl-3-methyl-3H-benzo b!furan-2-one were added to the composition instead of the compound of the invention cited above, similar but slightly less pronounced odor effects were observed.

EXAMPLE 5

Perfuming composition

A base perfuming composition was prepared by admixing the following ingredients

    ______________________________________                                         Ingredients         Parts by weight                                            ______________________________________                                         Synth. amber oil    100                                                        Bergamot essential oil                                                                             100                                                        Exaltex ®.sup.1)                                                                               80                                                         Iralia ®.sup.2) 100                                                        50%* Oakmoss absolute                                                                              270                                                        Crystalmoss         50                                                         Portugal Italy orange essential oil                                                                40                                                         Patchouli essential oil                                                                            70                                                         Bourbon vetyver essential oil                                                                      80                                                         Wardia ®.sup.3) 80                                                         TOTAL               970                                                        ______________________________________                                          *in dipropyleneglycol (DIPG)                                                   .sup.1) oxacyclohexadecan2-one; origin: Firmenich SA, Geneva, Switzerland      .sup.2) methylionone; origin: Firmenich SA, Geneva, Switzerland                .sup.3) origin: Firmenich SA, Geneva, Switzerland                        

When 30 parts by weight of 3-methyl-6-phenyl-3H-benzo b!furan-2-one were added to this base composition of the Chypre type, there was obtained a novel composition, the odor of which had acquired a distinct fruity-lactonic character reminiscent of the classical perfumes such as "Madame" of Rochas or "Champagne" of Yves St. Laurent.

On the other hand, when the effect imparted by this compound was compared to that obtained by adding to the base composition 30 parts by weight of γ-undecalactone, it became apparent that the resulting composition according to the invention possessed a more pronounced fruity, apricot type note, whereas that of the composition which contained γ-undecalactone possessed a weaker fruity character which was rather of the peach type. In addition, after 24 h, the fruity note was far more perceptible in the odor of the composition containing 3-methyl-6-phenyl-3H-benzo b!furan-2-one and a week later it was still persistent, without any change in its strength, whereas no fruity character could any longer be perceived in the odor of the composition which contained γ-undecalactone.

The addition of 30 parts by weight of 6-isopropyl-3-methyl-3H-benzo b!furan-2-one to the base composition provided a novel composition whose odor possessed a more marked lactonic character than in the case of the addition of its phenyl analogue, although the volume and the tenacity of the odor were nevertheless inferior. 

We claim:
 1. A method for imparting a fragrance to a composition or article which comprises adding to said composition or article a perfuming ingredient comprising a compound of formula ##STR8## wherein a. symbols R¹ to R⁴ represent hydrogen; orb. R¹ represents hydrogen, one of R², R³ or R⁴ represents a linear or branched alkyl radical having from 1 to 5 carbons, a methoxy group, a cycloaliphatic radical having 5 or 6 carbon atoms or a phenyl radical, and the others represent hydrogen; or c. R¹ represents hydrogen and two adjacent symbols among R² and R⁴ are identical or different and each represent a C¹ to C⁴ linear or branched alkyl radical or a methoxy group, with the other symbol representing hydrogen; or d. two non-adjacent symbols among R¹ to R⁴ represent hydrogen and the other two are identical or different and represent a C¹ to C⁴ linear or branched alkyl radical or a methoxy group; or e. two adjacent symbols among R¹ to R⁴ are taken together to represent a saturated or unsaturated ring having 5 or 6 carbon atoms, which ring can possess one or more methyl radicals as substituents, with the other two symbols representing hydrogen; or f. one of symbols among R¹ to R⁴ is hydrogen and the other three are identical and represent a methyl group;said compound added in an amount effective to impart, modify or enhance the odor character of said composition or article.
 2. The method according to claim 1 wherein the perfuming ingredient is a compound of formula ##STR9## wherein R² and R³ are identical or different and each represents a hydrogen atom, a C₁ to C₄ linear or branched alkyl radical, or a methoxy group.
 3. The method according to claim 1 wherein the perfuming ingredient is a compound of formula ##STR10## wherein R² and R⁴ are identical or different and each represents a hydrogen atom, a C₁ to C₄ linear or branched alkyl radical, or a methoxy group.
 4. The method according to claim 1 wherein the perfuming ingredient is 3,4,6-trimethyl-3H-benzo b!furan-2-one, 3,6,7-trimethyl-3H-benzo b!furan-2-one or 3,5,6,7-tetrahydro-3-methyl-indeno 5,6-b!furan-2-one.
 5. The method according to claim 1 wherein the perfuming ingredient is one of the following compounds:a. 3-methyl-3H-benzo b!furan-2-one; b. 3,6-dimethyl-3H-benzo b!furan-2-one; c. 6-ethyl-3-methyl-3H-benzo b!furan-2-one; d. 6-isopropyl-3-methyl-3H-benzo b!furan-2-one; e. 3-methyl-6-phenyl-3H-benzo b!furan-2-one; f. 6-methoxy-3-methyl-3H-benzo b!furan-2-one; g. 3-methyl-5-propyl-3H-benzo b!furan-2-one; h. 5-tert-butyl-3-methyl-3H-benzo b!furan-2-one; i. 3-methyl-5-(1-methylpropyl)-3H-benzo b!furan-2-one; or j. 3,5,6-trimethyl-3H-benzo b!furan-2-one.
 6. The method according to claim 3 wherein the perfuming ingredient is 5,7-diisopropyl-3-methyl-3H-benzo b!furan-2-one or 5,7-di-tert-butyl-3-methyl-3H-benzo b!furan-2-one.
 7. The method according to claim 6 wherein the perfuming ingredient is 5,7-di-tert-butyl-3-methyl-3H-benzo b!furan-2-one in admixture with 3-methyl-cyclopentadec-5-en-1-one.
 8. Perfuming composition or perfumed article containing as an active perfuming ingredient a compound of formula (I), (Ia) or (Ib) as defined in one of claims 1, 2 or
 3. 9. Perfuming composition or perfumed article containing as an active perfuming ingredient one of the compounds recited in one of claims 4, 5 or
 6. 10. Perfuming composition or perfumed article containing as an active perfuming ingredient the admixture of compounds recited in claim
 7. 11. Perfumed article produced by the method of claim 1 in the form of a perfume or cologne, a soap, a bath or shower gel, a shampoo or other hair care product, a cosmetic preparation, a body or air deodorant, a detergent, a fabric softener or a household product.
 12. A the compound selected from the group consisting of:a. 6-ethyl-3-methyl-3H-benzo b!furan-2-one; b. 6-isopropyl-3-methyl-3H-benzo b!furan-2-one; c. 3-methyl-5-propyl-3H-benzo b!furan-2-one; d. 5-tert-butyl-3-methyl-3H-benzo b!furan-2-one; e. 3-methyl-5-(1-methylpropyl)-3H-benzo b!furan-2-one; f. 3,4,6-trimethyl-3H-benzo b!furan-2-one; g. 3,5,6-trimethyl-3H-benzo b!furan-2-one; h. 3,6,7-trimethyl-3H-benzo b!furan-2-one; i. 3,5,6,7-tetrahydro-3-methyl-indeno 5,6-b!furan-2-one; j. 5,7-diisopropyl-3-methyl-3H-benzo b!furan-2-one; and k. 5,7-di-tert-butyl-3-methyl-3H-benzo b!furan-2-one. 